The present invention relates to a compound of formula 
wherein
R1 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents of the aryl and heteroaryl rings being selected from the group consisting of
OH, halogen, CN, NO2, C1-C6alkyl, C3-C8cycloalkyl, optionally substituted C3-C8cycloalkenyl, C1-C6alkyl-C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C6alkyl, C1-C6haloalkyl, C3-C8halocycloalkyl, C1-C6alkoxy, C3-C8cycloalkoxy, C1-C6haloalkoxy, C3-C8halocycloalkoxy, C1-C6alkylthio, C3-C8cycloalkylthio, C1-C6haloalkylthio, C3-C8halocycloalkylthio, C1-C6alkylsulfinyl, C3-C8cycloalkylsulfinyl, C1-C6haloalkylsulfinyl, C3-C8halocycloalkylsulfinyl, C1-C6alkylsulfonyl, C3-C8cycloalkylsulfonyl, C1-C6haloalkylsulfonyl, C3-C8halocycloalkylsulfonyl, optionally substituted C2-C8alkenyl, optionally substituted C2-C8alkynyl, C1-C6alkylcarbonyl, C1-C6alkyl-C(xe2x95x90NOR6), xe2x80x94P(xe2x95x90O)(OC1-C6alkyl)2, R7,
unsubstituted or mono- to penta-substituted phenyl, unsubstituted or mono- to penta-substituted heteroaryl; wherein the substituents of the said phenyl and heteroaryl radicals are selected from the group consisting of OH, halogen, CN, NO2, C1-C6alkyl, optionally substituted C2-C8alkenyl, optionally substituted C2-C8alkynyl, C3-C8cycloalkyl, optionally substituted C3-C8cycloalkenyl, C1-C6haloalkyl, C3-C8halocycloalkyl, C1-C6alkoxy, C3-C8cycloalkoxy, C1-C6haloalkoxy, C3-C8halocycloalkoxy, C1-C6alkylthio, C3-C8cycloalkylthio, C1-C6haloalkylthio, C3-C8halocycloalkylthio, C1-C6alkylsulfinyl, C3-C8cycloalkylsulfinyl, C1-C6haloalkylsulfinyl, C3-C8halocycloalkylsulfinyl, C1-C6alkylsulfonyl, C3-C8cycloalkylsulfonyl, C1-C6haloalkylsulfonyl, C3-C8halocycloalkylsulfonyl, C2-C8alkenyl, which is unsubstituted or substituted, C2-C8alkynyl, which is unsubstituted or substituted, C1-C6alkylcarbonyl, xe2x80x94CH(xe2x95x90NOR6), xe2x80x94C(C1-C6alkyl)(xe2x95x90NOR6), C1-C6alkyl-C(xe2x95x90NOR6), xe2x80x94CHO, xe2x80x94C(xe2x95x90O)xe2x80x94C1-C6alkyl and R7;
unsubstituted or mono- to penta-substituted phenoxy;
unsubstituted or mono- to penta-substituted phenylthio;
unsubstituted or mono- to penta-substituted phenylamino; and
unsubstituted or mono- to penta-substituted phenyl-(C1-C6alkyl)-amino;
the substituents of the phenoxy, phenylthio, phenylamino and phenyl-(C1-C6alkyl)-amino groups being selected from the group consisting of halogen, CN, NO2, C1-C6alkyl, C3-C8-cycloalkyl, C1-C6haloalkyl, C3-C8halocycloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C8cycloalkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, C3-C8cycloalkylthio, C1-C6haloalkylthio and C3-C8halocycloalkylthio;
R2 is H, OH, halogen, CN, NO2, optionally substituted C1-C6alkyl, C1-C6alkoxy, C1-C6alkoxy-C1-C6alkyl, C1-C6alkylthio, C1-C6alkylthio-C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl, C3-C8halocycloalkyl, xe2x80x94NHxe2x80x94C1-C6-alkyl, SH or CH2xe2x80x94NO2;
A is a single bond, C1-C12alkylene, O, O(C1-C12alkylene), S(O)n, S(O)n(C1-C12alkylene), C2-C8alkenylene, C2-C8alkynylene; NR3 or NR3(C1-C12alkylene);
R3 is H, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl, C2-C8alkenyl, C2-C8alkynyl, aryl-C1-C6alkyl, (CH2)pC(O)R4 or C1-C6alkoxy-C2-C6alkyl;
R4 is H, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl, C1-C6alkoxy, N(R5)2 or C1-C6alkoxy-C2-C6alkyl;
R5 is H, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl or aryl-C1-C6alkyl;
R6 is H, C1-C6alkyl, C3-C8cycloalkyl or xe2x80x94C(xe2x95x90O)xe2x80x94R5;
R7 is 
R8 and R9 are each independently of the other H or C1-C6alkyl;
X1 is R10;
X2 and X3 are each independently of the other H or R10;
R10 is halogen, CN, NO2, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl, C3-C8halocycloalkyl, C1-C6alkoxy, C3-C8cycloalkoxy, C1-C6haloalkoxy, C3-C8halocycloalkoxy, C1-C6alkylthio, C3-C8cycloalkylthio, C1-C6haloalkylthio or C3-C8halocycloalkylthio;
m is 1, 2, 3 or 4;
n is 0, 1 or 2; and
W is O or S;
with the proviso that the radical Axe2x80x94R1 and the phenyl group substituted by X1, X2 and X3 are not in the vicinal position relative to one another on the triazine ring,
with the further proviso, that X1 is not CH3, Cl or F, when X2 and X3 are H, A is a single bond, R1 is phenyl, 2-fluorophenyl, p-fluorophenyl or 3-chlorophenyl and R2 is H, Cl or NHC2xe2x80x94H5;
and with the exception of 3,6-di-(2-chlorophenyl)-5-hydroxy-1,2,4-triazine and
with the exception of 3-(2-methylphenyl)-6-(4-methylphenyl)-5-trifluoromethyl-1,2,4-triazine;
and to the physiologically tolerable and agrochemically acceptable addition compounds thereof, and where appropriate to E/Z isomers, to mixtures of E/Z isomers and/or to tautomers, in each case in free form or in salt form;
to a process for the preparation of those compounds and to their use, to pesticidal compositions in which the active ingredient is selected from those compounds, in each case in free form or in agrochemically acceptable salt form, and to a process for the manufacture of those compositions and to their use.
Preferred are compounds of the formula (I), wherein
R1 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, wherein the substituents are selected from the group consisting of OH, Halogen, CN, NO2, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Alkyl-C3-C8-cycloalkyl, C3-C8-Cycloalkyl-C1-C6-alkyl, C1-C6-Haloalkyl, C3-C8-Halocycloalkyl, C1-C6-Alkoxy, C3-C8-Cycloalkoxy, C1-C6-Haloalkoxy, C3-C8-Halocycloalkoxy, C1-C6-Alkylthio, C3-C8-Cycloalkylthio, C1-C6-Haloalkylthio, C3-C8-Halocycloalkylthio, C1-C6-Alkylsulfinyl, C3-C8-Cycloalkylsulfinyl, C1-C6-Haloalkylsulfinyl, C3-C8-Halocycloalkylsulfinyl, C1-C6-Alkylsulfonyl, C3-C8-Cycloalkylsulfonyl, C1-C6-Haloalkylsulfonyl, C3-C8-Halocycloalkylsulfonyl, C1-C8-Alkenyl, C2-C8-Alkinyl, C1-C6-Alkylcarbonyl, C1-C6-Alkyl-C(xe2x95x90NOR6), R7, is unsubstituted or mono- to penta-substituted phenyl, wherein the substituents are selected from the group consisting of OH, Halogen, CN, NO2, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Haloalkyl, C3-C8-Halocycloalkyl, C1-C6-Alkoxy, C3-C8-Cycloalkoxy, C1-C6-Haloalkoxy, C3-C8-Halocycloalkoxy, C1-C6-Alkylthio, C3-C8-Cycloalkylthio, C1-C6-Haloalkylthio, C3-C8-Halocycloalkylthio, C1-C6-Alkylsulfinyl, C3-C8-Cycloalkylsulfinyl, C1-C6-Haloalkylsulfinyl, C3-C8-Halocycloalkylsulfinyl, C1-C6-Alkylsulfonyl, C3-C8-Cycloalkylsulfonyl, C1-C6-Haloalkylsulfonyl, C3-C8-Halocycloalkylsulfonyl, C2-C8-Alkenyl, C2-C8-Alkinyl, C1-C6-Alkylcarbonyl, C1-C6-Alkyl-C(xe2x95x90NOR6) and R7; is unsubstituted or mono- to penta-substituted phenoxy, is unsubstituted or mono- to penta-substituted phenylthio, is unsubstituted or mono- to penta-substituted phenylamino and is unsubstituted or mono- to penta-substituted phenyl-(C1-C6-alkyl)-amino, wherein the substituents are selected from the group consisting of Halogen, CN, NO2, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Haloalkyl, C3-C8-Halocycloalkyl, C1-C6-Alkoxy, C3-C8-Cycloalkoxy, C1-C6-Alkylthio, C3-C8-Cycloalkylthio, C1-C6-Haloalkylthio and C3-C8-Halocycloalkylthio;
R2 is H, Halogen, CN, NO2, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Haloalkyl or C3-C8-Halocycloalkyl;
A is (CR11R12)p, O(CR11R12)p, S(O)n(CR11R12)p, unsubstituted or substituted C2-C8-Alkenylen, unsubstituted or substituted C2-C8-Alkinylen, wherein the substituents are selected from the group consisting of R1, and R12; or NR3(CH2)p;
R3 is H, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Haloalkyl, C2-C8-Alkenyl, C2-C8-Alkinyl, Aryl-C1-C6-alkyl, (CH2)pC(O)R4 or C1-C6-Alkoxy-C2-C6-alkyl;
R4 is H, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Haloalkyl, C1-C6-Alkoxy, N(R5)2 or C1-C6-Alkoxy-C2-C6-alkyl;
R5 is H, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Haloalkyl or Aryl-C1-C6-alkyl;
R6 is H, C1-C6-Alkyl or C3-C8-Cycloalkyl;
R7 is 
R8 and R9 are each independently of the other H or C1-C6-Alkyl;
X1 is R10;
X2 and X3 are each independently of the other H or R10;
R10 is Halogen, CN, NO2, C1-C6-Alkyl, C3-C8-Cycloalkyl, C1-C6-Haloalkyl, C3-C8-Halocycloalkyl, C1-C6-Alkoxy, C3-C8-Cycloalkoxy, C1-C6-Haloalkoxy, C3-C8-Halocycloalkoxy, C1-C6-Alkylthio, C3-C8-Cycloalkylthio, C1-C6-Haloalkylthio or C3-C8-Halocycloalkylthio;
R11 and R12 are each independently of the other H or C1-C6-Alkyl;
m 1, 2, 3 or 4;
n is 0, 1 or 2;
p is 0, 1, 2, 3, 4, 5 or 6; and
Q is O or S.
Certain 1,2,4-triazine derivatives are proposed in the literature as active ingredients in compositions for controlling pests on domestic animals and productive livestock and in crops of useful plants. The biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, for which reason there is a need to provide further compounds having pesticidal properties, that problem being solved according to the invention by the provision of the present compounds of formula (I). Because they contain at least three basic centres, the compounds of formula (I) may be in the form of salts or may form e.g. acid addition salts. The latter are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, e.g. halo-substituted, C1-C4alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo-substituted, C1-C4alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid. Hereinabove and hereinbelow any reference to the free compounds of formula (I) or to their salts is to be understood as including also the corresponding salts or the free compounds of formula (I), respectively, as appropriate and expedient, the free form being preferred.
The general terms used hereinabove and hereinbelow have the meanings given below, unless defined otherwise.
Unless defined otherwise, carbon-containing groups and compounds each contain from 1 up to and including 6, preferably from 1 up to and including 4, more especially 1 or 2, carbon atoms.
Aryl is phenyl or naphthyl.
Heteroaryl is especially pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, indolyl or indazolyl, which are preferably bonded via a carbon atom; thiazolyl, benzofuranyl, benzothiazolyl or indolyl, especially thiazolyl or indolyl, is preferred.
Halogenxe2x80x94both as a group per se and as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthioxe2x80x94is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
Alkylxe2x80x94both as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthioxe2x80x94is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Cycloalkylxe2x80x94both as a group per se and as a structural element of other groups and compounds, such as halocycloalkyl, cycloalkoxy and cycloalkylthioxe2x80x94is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Alkenylxe2x80x94both as a group per se and as a structural element of other groups and compoundsxe2x80x94is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight-chained, e.g. allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1,3-hexadienyl or 1,3-octadienyl, or branched, e.g. isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl.
Alkynylxe2x80x94both as a group per se and as a structural element of other groups and compoundsxe2x80x94is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight-chained, e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1,5-heptadien-3-ynyl, or branched, e.g. 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2-ynyl or 2-methylhept-3-ynyl.
Alkylene, alkenylene and alkynylene are straight-chained or branched bridge members, especially xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH(CH3)xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH2C(CH3)2xe2x80x94CH2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94; xe2x80x94Cxe2x89xa1Cxe2x80x94, and xe2x80x94CH2Cxe2x89xa1Cxe2x80x94; more especially xe2x80x94CH2xe2x80x94.
Halo-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio, may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different. Examples of haloalkylxe2x80x94both as a group per se and as a structural element of other groups and compounds, such as haloalkoxy and haloalkylthioxe2x80x94are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CFCl2, CF2CHBr2, CF2CHClF, CF2CHBrF or CClFCHClF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or an isomer thereof substituted from one to nine times by fluorine, chorine and/or bromine, such as CF(CF3)CHFCF3 or CH2(CF2)2CF3; pentyl or an isomer thereof substituted from one to eleven times by fluorine, chlorine and/or bromine, such as CF(CF3)(CHF)2CF3 or CH2(CF2)3CF3; and hexyl or an isomer thereof substituted from one to thirteen times by fluorine, chlorine and/or bromine, such as (CH2)4CHBrCH2Br, CF2(CHF)4CF3, CH2(CF2)4CF3 or C(CF3)2(CHF)2CF3.
Optionally substituted radicals such as for instance C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkenyl or C1-C6alkyl, are preferrably substituted with OH, CN, nitro, halogen, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, phenyl, halogenphenyl, phenoxy, NHR3, xe2x80x94C(xe2x95x90O)NH2, xe2x80x94C(xe2x95x90O)Oxe2x80x94C1-C6-alkyl and xe2x80x94C(xe2x95x90O)xe2x80x94C1-C6-alkyl.
Preferred embodiments within the scope of the invention, taking into account the proviso mentioned above, are a compound of formula (I):
(1) wherein R1 is an unsubstituted or mono- to tri-substituted aryl or heteroaryl ring, the substituents being selected from the group consisting of OH, halogen, CN, NO2, C1-C4alkyl, C3-C6cycloalkyl, optionally substituted C5-C6cycloalkenyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, optionally substituted C2-C6alkenyl, optionally substituted C2-C6alkynyl, C1-C4alkylcarbonyl, unsubstituted or mono- to penta-substituted phenyl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl and C1-C4alkylcarbonyl, and unsubstituted or mono- to penta-substituted phenoxy or unsubstituted or mono- to penta-substituted phenylamino, the substituents of the phenoxy- and phenylaminogroup being selected from the group consisting of halogen, CN, NO2, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4halo-alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, and C1-C4haloalkylthio;
especially mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, CN, NO2, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy, C1-C2haloalkoxy, unsubstituted or mono- or di-substituted phenyl, the substituents of the said phenyl being selected from the group consisting of halogen, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy, C1-C2haloalkoxy, C1-C2alkylthio and C1-C2haloalkylthio; and phenoxy;
more especially mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, methyl, halomethyl, methoxy, halomethoxy, unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, methyl, halomethyl, methoxy, halomethoxy, methylthio and halomethylthio; and phenoxy;
especially wherein R1 is a phenyl ring, which is monosubstituted by mono- or di-substituted phenyl, which is preferably in the 4-position, the substituents on the mentioned phenyl radical being selected from the group consisting of halogen, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio and trifluoromethylthio;
(2) wherein R2 is H, halogen or C1-C4alkyl, especially H or C1-C4alkyl, more especially H;
(3) a compound of formula (I) wherein
A is a single bond, C1-C4alkylene, O, OCH2, C2-C4alkenylene, C2-C4alkynylene or NR3, especially a single bond, O, OCH2, Cxe2x89xa1C, CHxe2x95x90CH or NH, more especially a single bond;
(4) wherein R3 is H, C1-C6alkyl or C1-C6haloalkyl, especially H or C1-C6alkyl, more especially H or C1-C2alkyl, especially H;
(5) wherein X1 is halogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio or C1-C4haloalkylthio; especially halogen, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy or C1-C2haloalkoxy; more especially fluorine, chlorine, methyl, trifluoromethyl or methoxy, especially fluorine or chlorine, more especially fluorine;
(6) wherein X2 is H, halogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio or C1-C4haloalkylthio; especially H, halogen, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy or C1-C2haloalkoxy; more especially fluorine, chlorine, methyl, trifluoromethyl or methoxy, especially fluorine or chlorine, more especially fluorine;
(7) wherein X3 is H, halogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio or C1-C4haloalkylthio; especially H, halogen, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy or C1-C2haloalkoxy; more especially fluorine, chlorine, methyl, trifluoromethyl or methoxy, especially H, fluorine or chlorine, preferably H;
(8) wherein the phenyl group substituted by X1, X2 and X3 is in the 3-position on the triazine ring;
(9) wherein R1 is an unsubstituted or mono- to tri-substituted aryl or heteroaryl ring, the substituents being selected from the group consisting of OH, halogen, CN, NO2, C1-C4alkyl, C3-C6cycloalkyl, optionally substituted C5-C6cycloalkenyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, optionally substituted C2-C6alkenyl, optionally substituted C2-C6alkynyl, C1-C4alkylcarbonyl, unsubstituted or mono- to penta-substituted phenyl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl and C1-C4alkylcarbonyl, unsubstituted or mono- to penta-substituted phenoxy, and unsubstituted or mono- to penta-substituted phenylamino, the substituents being selected from the group consisting of halogen, CN, NO2, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfonyl and C1-C4haloalkylsulfonyl;
R2 is H, halogen or C1-C4alkyl;
A is a single bond, C1-C6alkylene, O(C1-C6alkylene), C2-C4alkenylene, C2-C4alkynylene or NR3;
R3 is H, C1-C6alkyl or C1-C6haloalkyl;
X1 is halogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio or C1-C4haloalkylthio;
X2 and X3 are each independently of the other H, halogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio or C1-C4haloalkylthio; and
the phenyl group substituted by X1, X2 and X3 is in the 3-position on the triazine ring;
(11) wherein R1 is mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, CN, NO2, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy, C1-C2haloalkoxy, unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy, C1-C2haloalkoxy, C1-C2alkylthio and C1-C2haloalkylthio, and phenoxy;
R2 is H or C1-C4alkyl;
A is a single bond, O, OCH2, Cxe2x80x94C, CHxe2x95x90CH or NH;
X1 is halogen, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy or C1-C2haloalkoxy;
X2 and X3 are each independently of the other H, halogen, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy or C1-C2haloalkoxy; and
the phenyl group substituted by X1, X2 and X3 is in the 3-position on the triazine ring;
(12) wherein R1 is mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, methyl, halomethyl, methoxy, halomethoxy, unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, methyl, halomethyl, methoxy, halomethoxy, methylthio and halomethylthio; and phenoxy;
R2 is H;
A is a single bond;
X1 is fluorine, chlorine, methyl, trifluoromethyl or methoxy;
X2 and X3 are each independently of the other H, fluorine, chlorine, methyl, trifluoromethyl or methoxy; and
the phenyl group substituted by X1, X2 and X3 is in the 3-position on the triazine ring;
in each case including the physiologically tolerable addition compounds.
(13) wherein the group Axe2x80x94R1 is in the 6-position on the triazine ring.
Within the scope of the invention preference is given especially to the compounds of formula (I) listed in Tables 1 to 6 and more especially to the compounds of formula (I) mentioned in the Synthesis Examples.
The invention relates also to a process for the preparation of the compounds of formula (I), in each case in free form or in salt form, which comprises, for example,
a) for the preparation of a compound of formula (I) wherein A is a single bond and the phenyl group substituted by X1, X2 and X3 is in the 6-position on the triazine ring, reacting a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which X1, X2, X3 and R2 are as defined for formula (I) and Q is a leaving group, with two equivalents of a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which R1 is as defined for formula (I), optionally in the presence of a catalyst, preferably silver acetate, or
b) for the preparation of a compound of formula (I) wherein A is a single bond and the phenyl group substituted by X1, X2 and X3 is in the 3-position on the triazine ring, reacting two equivalents of a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which X1, X2 and X3 are as defined for formula (I), with one equivalent of a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which R1 and R2 are as defined for formula (I) and Q1 is a leaving group, optionally in the presence of a catalyst, preferably silver acetate, or
c) for the preparation of a compound of formula (I) wherein A has the meanings defined for formula (I) with the exception of a single bond, reacting a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which X1, X2, X3 and R2 are as defined for formula (I) and Q2 is a leaving group, with a compound of formula
R1xe2x80x94Axe2x80x94Mxe2x80x83xe2x80x83(VII), 
which is known or can be prepared analogously to corresponding known compounds and in which R1 is as defined for formula (I) and A has the meanings defined for formula (I) with the exception of S(O), S(O)(C1-C12alkylene), S(O)2 and S(O)2(C1-C12alkylene), and M is hydrogen, a transition metal or an alkali metal, and when A is S or S(C1-C12alkylene), if desired oxidising the resulting product, optionally after intermediate isolation, for the preparation of a compound of formula (I) wherein A is S(O), S(O)(C1-C12alkylene), S(O)2 or S(O)2(C1-C12alkylene), or
d) for the preparation of a compound of formula (i) wherein A is a single bond, oxidising a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which X1, X2, X3 and R2 are as defined for formula (I), with an oxidising agent and reacting the resulting product, optionally after intermediate isolation, with a compound of formula (III) and reacting the resulting product, optionally after intermediate isolation, with an ammonium salt, preferably ammonium acetate, or
e) for the preparation of a compound of formula (I) wherein the phenyl group substituted by X1, X2 and X3 is in the 3-position on the triazine ring, reacting a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which R1 and R2 are as defined for formula (I) and Q3 is O or NOH, with a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which X1, X2 and X3 are as defined for formula (I) and Q4 is H or a protecting group capable of being removed, in free form or in salt form, or
f) for the preparation of a compound of formula (I) wherein A is C1-C12alkylene, C2-C8alkenylene or C2-C8alkynylene, reacting a compound of formula (VI), which is known or can be prepared analogously to corresponding known compounds and in which X1, X2, X3 and R2 are as defined for formula (I) and Q2 is C1-C6alkyl, preferably methyl, with a compound of formula
R1xe2x80x94C1-C10alkyl-CHOxe2x80x83xe2x80x83(XI), 
which is known or can be prepared analogously to corresponding known compounds and in which R1 is as defined for formula (I), optionally in the presence of a strong base catalyst, preferably lithium diethylamide or butyllithium, and dehydrating the resulting product, optionally after intermediate isolation, optionally in the presence of a strong acid, and, if desired, for the preparation of a compound of formula (I) wherein A is C1-C12alkylene, carrying out hydrogenation in the presence of a hydrogenation catalyst, or for the preparation of a compound of formula (I) wherein A is C2-C8alkynylene, carrying out reaction with a halogen and then with a strong base, preferably NaOH; or
g) for the preparation of a compound of formula (I) wherein the phenyl ring substituted by the substituents X is in the 3-position and AR1 is in the 6-position, reacting a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which X1, X2 and X3 are as defined for formula (I) and W is O or S, or a salt thereof, with a compound of formula 
which is known or can be prepared analogously to corresponding known compounds and in which A, R1 and R2 are as defined for formula (I);
and in each case, if desired, converting a compound of formula (I), in each case in free form or in salt form, obtainable in accordance with the process or by another method into a different compound of formula (I), separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula (I) obtainable in accordance with the process into a salt or converting a salt of a compound of formula (I) obtainable in accordance with the process into the free compound of formula (I) or into a different salt.
The comments made above in connection with salts of compounds of formula (I) apply analogously, in respect of their salts, to starting materials mentioned hereinabove and hereinbelow.
In the individual process steps the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof.
Variant a):
Examples of solvents and diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoric acid triamide; nitrites, such as acetonitrile and propionitrile; and sulfoxides, such as dimethyl sulfoxide.
Preferred leaving groups are halogens, tosylates, mesylates and triflates, especially halogens, more especially chlorine.
The reaction is advantageously effected in a temperature range of from about 0xc2x0 C. to about +150xc2x0 C., preferably from about 20xc2x0 C. to about +100xc2x0 C.
In a preferred embodiment of variant a), a compound of formula (II) is reacted with a compound of formula (III) at from about 50xc2x0 to about 100xc2x0, preferably about 85xc2x0, in an ether, preferably ethylene glycol dimethyl ether, in the presence of a catalyst, preferably silver acetate.
Variant b):
Examples of solvents and diluents are given under variant a).
Preferred leaving groups are halogens, tosylates, mesylates and triflates, especially halogens, more especially chlorine.
The reaction is advantageously effected in a temperature range of from about 0xc2x0 C. to about +150xc2x0 C., preferably from about 20xc2x0 C. to about +100xc2x0 C.
In a preferred embodiment of variant b), a compound of formula (IV) is reacted with a compound of formula (V) at from about 50xc2x0 C. to about 100xc2x0 C., preferably about 85xc2x0, in an ether, preferably ethylene glycol dimethyl ether, in the presence of a catalyst, preferably silver acetate.
Variant c):
Examples of solvents and diluents are given under variant a).
Preferred leaving groups are OH, halogens, tosylates, mesylates and triflates, especially halogens, more especially bromine and chlorine.
The reaction is advantageously effected in a temperature range of from about 0xc2x0 C. to about +150xc2x0 C., preferably from about 20xc2x0 C. to about +100xc2x0 C.
In a preferred embodiment of variant c), a compound of formula (VI) is reacted with a compound of formula (VII) at from about 0xc2x0 to about 100xc2x0, preferably about 20xc2x0, in an inert solvent, optionally in the presence of a base as catalyst.
Variant d):
Examples of solvents and diluents are given under variant a).
Preferred oxidising agents are halogens, more especially bromine.
The reactions are advantageously effected in a temperature range of from about 0xc2x0 C. to about +120xc2x0 C., preferably from about 0xc2x0 C. to about +80xc2x0 C.
In a preferred embodiment of variant d), a compound of formula (VII) is oxidised with bromine at from about 0xc2x0 to about 100xc2x0, preferably about 80xc2x0, in a polar solvent, preferably DMSO/water, and then, after intermediate isolation of the resulting diketo compound, reacted with a compound of formula (III) at from about 0xc2x0 to about 60xc2x0, preferably about 20xc2x0, in a polar solvent, preferably an alcohol, and then, preferably without intermediate isolation, reacted with ammonium acetate at from about 0xc2x0 to about 120xc2x0, preferably about 100xc2x0, in a polar solvent, preferably glacial acetic acid.
Variant e):
Examples of solvents and diluents are given under variant a).
Preferred protecting groups are C1-C6alkoxycarbonyl.
The reactions are advantageously effected in a temperature range of from about 0xc2x0 C. to about +150xc2x0 C., preferably from about 0xc2x0 C. to about +120xc2x0 C.
In a preferred embodiment of variant e), a compound of formula (IX) is reacted with a compound of formula (X) at from about 0xc2x0 to about 100xc2x0, preferably about 20xc2x0, in an alcohol, preferably ethanol or an ethanol/water mixture, optionally in the presence of an acid catalyst, preferably formic acid.
Variant f):
Examples of solvents and diluents are given under variant a).
The reactions are advantageously effected in a temperature range of from about xe2x88x9280xc2x0 C. to about +150xc2x0 C., preferably from about 0xc2x0 C. to about +110xc2x0 C.
In a preferred embodiment of variant f), a compound of formula (VI) wherein Q2 is methyl is reacted with an aldehyde of formula (XI) at from about xe2x88x9280xc2x0 C. to about 0xc2x0 C., preferably about xe2x88x9270xc2x0 C., in a non-polar solvent, preferably tetrahydrofuran, in the presence of a strong base, preferably n-butyllithium, and then, preferably after intermediate isolation, reacted with a strong acid, preferably toluenesulfonic acid, at from about 80xc2x0 C. to about 150xc2x0 C., preferably at the boiling temperature of the solvent, in a non-polar solvent, preferably toluene.
Variant g):
Examples of solvents and diluents are given under variant a); alcohols, such as methanol, ethanol and n-propanol, and also amides, such as dimethylformamide and dimethylacetamide, are especially suitable.
The reactions are advantageously effected in a temperature range of from about room temperature to the boiling point of the solvent used, preferably from about 60xc2x0 C. to about +100xc2x0 C.
In a preferred embodiment of variant g), a compound of formula (XII) wherein W is S is reacted with a compound of formula (XIII) at from about 25xc2x0 C. to about 100xc2x0 C., preferably at about 100xc2x0 C., in an alcohol, preferably in n-propanol.
Salts of compounds of formula (I) can be prepared in a manner known per se. For example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases by treatment with a suitable base or a suitable ion exchange reagent.
Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner; acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I); acid addition salts can be converted, for example, into other acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt that forms, for example silver chloride, is insoluble and thus precipitates out from the reaction mixture.
Depending upon the procedure and reaction conditions, compounds of formula (I) having salt-forming properties may be obtained in free form or in the form of salts.
The compounds of formula (I) may also be obtained in the form of solvates, especially in the form of their hydrates.
The invention relates to all those forms of the process in which a compound obtainable as starting compound or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out or a starting material is used in the form of a derivative or salt or, especially, is formed under the reaction conditions.
In the process of the present invention it is preferable to use those starting materials and intermediates which result in the compounds of formula (I) described at the beginning as being especially valuable.
The invention relates especially to the processes described in the Preparation Examples.
The invention relates also to novel starting materials and intermediates, in each case in free form or in salt form, used according to the invention for the preparation of the compounds of formula (I) and their salts, to their use and to processes for their preparation.
In the area of pest control, the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum, even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. The active ingredients according to the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina. The insecticidal, ovicidal and/or acaricidal action of the active ingredients according to the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60%.
The said animal pests include, for example, those mentioned in European Patent Application EP-A-736 252. The pests listed therein are therefore included by reference in the subject matter of the present invention;
representatives of the order Acarina are especially
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.
The compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.
Target crops include both natural crops and crops that have been modified by breeding or genetic methods, especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g. strawberries, raspberries and blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
The compounds according to the invention are especially suitable for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, citrus, maize, soybean, rape and vegetable crops.
Further areas of use of the compounds according to the invention are the protection of stored goods and stocks and of material, and also in the hygiene sector, especially in the protection of warm-blooded animals, including farm animals, such as cows, pigs, sheep and goats, poultry, such as hens, turkeys and geese, animals bred for their fur, such as mink, foxes, chinchillas, rabbits and the like, and also domestic animals and pets, such as cats and dogs, and even human beings, against pests of the mentioned type.
For example, flea infestation in domestic animals and pets is a problem for the animal owner to which there have as yet been found only unsatisfactory solutions. Owing to the complicated life cycle of the flea, none of the known methods of controlling fleas is totally satisfactory, especially since most of the known methods are aimed principally at controlling the fully grown fleas in the coat and take no account at all of the various juvenile stages of the fleas, which live not only in the animal""s coat, but also on the floor, on carpets, on the animal""s sleeping place, on chairs, in the garden and in all the other places with which the infested animal comes into contact. Flea treatment is generally expensive and must be continued for a prolonged period, success generally only being achieved when the treatment is applied not only to the affected animal, e.g. the dog or cat, but also simultaneously to any places frequented by the affected animal.
The compounds of formula (I) according to the invention can be used alone or in combination with other biocides. For example, in order to increase the effect they can be combined with pesticides having the same direction of action or in order to broaden the spectrum of action they can be combined with substances having a different direction of action. Where it is desired to extend the spectrum of action to endoparasites, e.g. worms, the compounds of formula (I) are advantageously combined with substances having endoparasiticidal properties. They can of course also be used in combination with anti-bacterial agents. Since the compounds of formula (I) are xe2x80x9cadulticidesxe2x80x9d, that is to say they are effective especially against the fully grown stages of the target parasites, the addition of pesticides that are more effective against the juvenile stages of the parasite may be very advantageous, since in this way the entire spectrum of the parasite population will be reached and, furthermore, a substantial contribution is made to avoiding the development of resistance.
The good pesticidal activity of the compounds of formula (I) according to the invention corresponds to a mortality of at least 50-60% of the mentioned pests.
The action of the compounds according to the invention and the compositions comprising them against animal pests can be significantly broadened and adapted to the given circumstances by the addition of other insecticides and/or acaricides. Suitable additives include, for example, representatives of the following classes of active ingredient: organophosphorus compounds, nitrophenols and derivatives, formamidines, thioureas, benzoylureas, carbamates, pyrethroids, neonicotinoids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
Especally suitable mixing partners are: Azamethiphos; Chlorfenvinphos; Cypermethrin, Cypermethrin high-cis; Cyromazin; Diafenthiuron; Diazinon; Dichlorvos; Dicrotophos; Dicyclanil; Fenoxycarb; Fluazuron; Furathiocarb; Isazofos; Jodfenphos; Kinoprene; Lufenuron; Methacriphos; Methidathion; Monocrotophos; Phosphamidon; Profenofos; Diofenolan; o compound obtainable from Bacillus thuringiensis strain GC91 or from NCTC11821; Pymetrozine; Bromopropylate; Methoprene; Disulfuton; Quinalphos; Tau-Fluvalinate; Thiocyclam; Thiometon; Aldicarb; Azinphos-methyl; Benfuracarb; Bifenthrin; Buprofezin; Carbofuran; Cartap; Chlorfluazuron; Chlorpyrifos; Cyfluthrin; Lambda-Cyhalothrin; Alpha-cypermethrin; zeta-Cypermethrin; Deltamethrin; Diflubenzuron; Endosulfan; Ethiofencarb; Fenitrothion; Fenobucarb; Fenvalerate; Formothion; Methiocarb; Heptenophos; Imidacloprid; lsoprocarb; Methamidophos; Methomyl; Mevinphos; Parathion; Parathion-methyl; Phosalone; Pirimicarb; Propoxur; Teflubenzuron; Terbufos; Triazamate; Abamectin; Fenobucarb; Tebufenozide; Fipronil; beta-Cyfluthrin; Silafluofen; Fenpyroximate; Pyridaben; Fenazaquin; Pyriproxyfen; Pyrimidifen; Nitenpyram; NI-25, Acetamiprid; Avermectin B1 (Abamectin); an insecticidally active extract of a plant; a preparation containing a nematocidally active component; a compound obtainable from Bacillus subtilis; a preparation containing insecticidally active fungi; a preparation containing an insecticidally active virus; AC 303 630; Acephate; Acrinathrin; Alanycarb; Alphamethrin; Amitraz; AZ 60541; Azinphos A; Azinphos M; Azocyclotin; Bendiocarb; Bensultap; Betacyfluthrin; BPMC; Brofenprox; Bromophos A; Bufencarb; Butocarboxin; Butylpyridaben; Cadusafos; Carbaryl; Carbophenothion; Chloethocarb; Chlorethoxyfos; Chlormephos; Cis-Res-methrin; Clocythrin; Clofentezin; Cyanophos; Cycloprothrin; Cyhexatin; Demeton M; Demeton S; Demeton-S-methyl; Dichlofenthion; Dicliphos; Diethion; Dimethoat; Dimethylvinphos; Dioxathion; Edifenphos; Emamectin; Esfenvalerat; Ethion; Ethofenprox; Ethoprophos; Etrimphos; Fenamiphos; Fenbutatinoxid; Fenothiocarb; Fenpropathrin; Fenpyrad; Fenthion; Fluazinam; Flucycloxuron; Flucythrinat; Flufenoxuron; Flufenprox; Fonophos; Fosthiazat; Fubfenprox; HCH; Hexaflumuron; Hexythiazox; Iprobenfos; Isofenphos; Isoxathion; Ivermectin; Lambda-cyhalothrin; Malathion; Mecarbam; Mesulfenphos; Metaldehyd; Metolcarb; Milbemectin; Moxidectin; Naled; NC 184; Omethoat; Oxamyl; Oxydemethon M; Oxydeprofos; Permethrin; Phenthoat; Phorat; Phosmet; Phoxim; Pirimiphos M; Pirimiphos A; Promecarb; Propaphos; Prothiofos; Prothoat; Pyrachlophos; Pyrada-phenthion; Pyresmethrin; Pyrethrum; RH 5992; Salithion; Sebufos; Sulfotep; Sulprofos; Tebufenpyrad; Tebupirimphos; Tefluthrin; Temephos; Terbam; Tetrachlor-vinphos; Thiacloprid; Thiamethoxam; Thiafenox; Thiodicarb; Thiofanox; Thionazin; Thuringiensin; Tralomethrin; Triarthen; Triazophos; Triazuron; Trichlorfon; Triflumuron; Trimethacarb; Vamidothion; Xylylcarb; YI 5301/5302; Zetamethrin; DPX-MP062; RH-2485; D 2341 or XMC (3,5,-Xy-lyl Methylcarbamate).
The compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula (I), or a combination of that active ingredient with other agrochemical active ingredients and, as appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants) and the invention relates also thereto.
The invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and the prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type. Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
A preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the frequency and the rate of application being dependent upon the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) by impregnating the locus of the plants with a liquid formulation or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In the case of paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
The crop protection agents of the invention are also suitable for protecting vegetative reproductive material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from animal pests. The reproductive material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown. The active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition. The composition can also be given when the reproductive material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow. The treatment procedures for vegetative reproductive material and the vegetative reproductive material thus treated are further objects of the invention.
As formulation auxiliaries there are used, for example, solid carriers, solvents, stabilisers, xe2x80x9cslow releasexe2x80x9d auxiliaries, dyes and optionally surface-active substances (surfactants). Suitable carriers and auxiliaries include all those substances customarily used in plant protection compositions. Suitable auxiliaries, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other auxiliaries in the compositions used according to the invention, include e.g. those described in EP-A-736 252; they are included by reference in the subject matter of the present invention.
Suitable anionic surfactants include both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurine salts as surfactants.
More frequently, however, so-called synthetic surfactants are used, as mentioned in EP-A-736 252, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives and alkylarylsulfonates.
The compounds of formula (I) are distinguished inter alia also by excellent activity against fleas, not only adult fleas being rapidly killed but also, by a circuitous route, the juvenile stages of the fleas. Flea larvae hatching out from the flea eggs feed substantially on the excreta of the adult fleas. Since the compounds of formula (I) according to the invention kill the adult fleas very rapidly, the necessary excreta are missing and the juvenile stages are deprived of the nutrient medium, so that they perish before reaching the adult stage.
The present invention therefore relates preferably to a method of controlling parasites on human beings, domestic animals, productive livestock and pets, wherein an effective amount of a composition comprising at least one compound of formula (I), or a physiologically tolerable salt thereof, is administered systemically or, preferably, topically to the warm-blooded animal.
The long-term action is achieved by the compounds of formula (I) according to the invention with various forms of administration, for example by administering the active ingredient in a formulated form externally or internally to the animal to be treated. xe2x80x9cFormulatedxe2x80x9d in this case means, for example, in the form of a powder, a tablet or granules, in liposomes or a capsule, in the form of an emulsion, a foam or a spray, in microencapsulated form or in pour-on or spot-on form. It will be understood that all orally administrable compositions comprise, in addition to customary formulation substances, further additives that encourage the host animal to take the composition orally voluntarily, e.g. suitable odorants and flavourings.
Percutaneous administration, e.g. by subcutaneous or intramuscular injection or as a depot preparation in the form of an implant, and topical application, for example in pour-on or spot-on form, represent preferred subjects of this invention on account of their being easy to carry out. A further mode of administration is oral administration, e.g. in the form of a tablet. Percutaneous and topical forms of administration are of particular interest and give excellent results.
Percutaneous forms of administration include, for example, subcutaneous, intramuscular and even intravenous administration of injectable forms. In addition to the customary syringes with needles, it is also possible to use needle-less high-pressure syringe devices.
Pour-on and spot-on formulations are especially preferred as topical forms of administration, but administration in the form of sprays, ointments, solutions or powders may also be expedient.
By selection of a suitable formulation, it is possible to enhance the ability of the active ingredients to penetrate the living tissue of the host animal and/or to maintain their availability. That is important when, for example, more sparingly soluble active ingredients are used, the low solubility of which requires means for enhancing solubility, since in such cases the animal""s body fluid is capable of dissolving only small amounts of active ingredients at a time.
Furthermore, in order to obtain a strongly delayed release of active ingredient, a compound of formula (I) according to the invention may also be present in a matrix formulation which physically prevents the active ingredient from being released and excreted prematurely and maintains the bioavailability of the active ingredient. Such a matrix formulation is injected into the body, e.g. intramuscularly or subcutaneously, and remains there as a form of depot from which the active ingredient is released continuously. Such matrix formulations are known to a person skilled in the art. They are generally wax-like, semi-solid substances, for example vegetable waxes and polyethylene glycols having a high molecular weight, or solid polymer formulations, for example so-called microspheres.
The rate of release of the active ingredient from the implant and thus the period of time over which the implant exhibits an action is generally determined by the accuracy with which the implant has been calibrated (amount of active ingredient in the implant), the environment around the implant and the polymer formulation from which the implant has been made.
The administration of veterinary medicinal additives to animal feed is well known in the field of animal health. It is usual first to prepare a so-called premix in which the active ingredient is dispersed in a liquid or is in finely divided form in solid carriers. That premix can normally comprise about 1 to 800 mg of compound per kg of premix, depending on the desired final concentration in the food.
Since the compounds of formula (I) according to the invention may be hydrolysed by the constituents of the food, they should be formulated in a protective matrix, for example in gelatin, before being added to the premix.
The present invention accordingly relates also to the aspect of controlling parasites by administering to the host animal with its food a compound of formula (I) that has been protected against hydrolysis.
A compound of formula (I) according to the invention is advantageously administered in a dose of from 0.01 to 800 mg/kg, preferably from 0.1 to 200 mg/kg, especially from 0.5 to 30 mg/kg, body weight, based on the host animal.
A good dose that can be routinely administered to the host animal is from 0.5 to 100 mg/kg, especially from 0.1 to 40 mg/kg, body weight. The administration is effected at suitable intervals in dependence upon the mode of administration and body weight.
The total dose may vary from one species of animal to another and also within a species of animal for the same active ingredient, since it depends inter alia on the weight, age and constitution of the host animal.
When used according to the invention, the compound of formula (I) according to the invention will normally be administered not in pure form but, preferably, in the form of a composition that comprises, in addition to the active ingredient, constituents that assist administration, suitable constituents being those that are tolerated by the host animal. It is of course possible, as well as controlling the adult parasites in accordance with the invention, additionally to use conventional methods to control the juvenile stages of the fleas, although the latter is not absolutely essential.
Such compositions to be administered in accordance with the invention generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of a compound of formula (I) according to the invention and from 99.9 to 1% by weight, especially from 99.9 to 5% by weight, of a solid or liquid, physiologically tolerable carrier, including from 0 to 25% by weight, especially from 0.1 to 25% by weight, of a non-toxic dispersant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
Such formulations may also comprise further auxiliaries, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
The physiologically tolerable carriers known from veterinary medicinal practice for oral, percutaneous and topical administration can be used as formulation auxiliaries. Some examples are given below.
Suitable carriers are especially fillers, such as sugars, e.g. lactose, saccharose, mannitol or sorbitol, cellulose preparations and/or calcium phosphates, for example tricalcium phosphate or calcium hydrogen phosphate, and binders, such as starch pastes using, for example, maize, wheat, rice or potato starch, gelatin, tragacanth, methylcellulose and/or, if desired, disintegrators, such as the above-mentioned starches, also carboxymethyl starch, cross-linked polyvinylpyrrolidone, agar, alginic acid or a salt thereof, such as sodium alginate. Adjuvants are especially flow conditioners and lubricants, for example silicic acid, talc, stearic acid or salts thereof, such as magnesium or calcium stearate, and/or polyethylene glycol. Dragxc3xa9e cores can be provided with suitable, optionally enteric, coatings, there being used inter alia concentrated sugar solutions which may comprise gum arabic, talc, polyvinylpyrrolidone, polyethylene glycol and/or titanium dioxide, or coating solutions in suitable organic solvents or solvent mixtures, or, for the preparation of enteric coatings, solutions of suitable cellulose preparations, such as acetylcellulose phthalate or hydroxypropylmethylcellulose phthalate. Dyes, flavourings or pigments may be added to the tablets or dragee coatings, for example for identification purposes or to indicate different doses of active ingredient.
Other orally administrable preparations are hard gelatin capsules, and also soft sealed capsules made of gelatin and a plasticiser, such as glycerol or sorbitol. The hard gelatin capsules may comprise the active ingredient in the form of granules, for example in admixture with fillers, such as lactose, binders, such as starches, and/or glidants, such as talc or magnesium stearate, and, if desired, stabilisers. In soft capsules, the active ingredient is preferably dissolved or suspended in suitable liquids, such as fatty oils, paraffin oil or liquid polyethylene glycols, to which stabilisers may likewise have been added. Preference is given inter alia to capsules that may either easily be bitten through or swallowed without being chewed.
The pour-on or spot-on method comprises applying the compound of formula (I) to a locally defined area of the skin or coat, advantageously on the back of the neck or the backbone of the animal. This is carried out, for example, by applying a swab or spray of the pour-on or spot-on formulation to a relatively small area of the coat from where the active ingredient becomes distributed over a wide area of the coat almost automatically as a result of the spreading constituents of the formulation assisted by the movements of the animal.
Pour-on and spot-on formulations advantageously comprise carriers that assist rapid distribution over the surface of the skin and in the coat of the host animal and are generally termed spreading oils. There are suitable, for example, oily solutions; alcoholic and isopropanolic solutions, e.g. solutions of 2-octyl dodecanol or oleyl alcohol; solutions in esters of monocarboxylic acids, such as isopropyl myristate, isopropyl palmitate, lauric acid oxalic ester, oleic acid oleyl ester, oleic acid decyl ester, hexyl laurate, oleyl oleate, decyl oleate, caproic acid esters of saturated fatty alcohols of chain length C12-C18; solutions of esters of dicarboxylic acids, such as dibutyl phthalate, diisopropyl isophthalate, adipic acid diisopropyl ester, di-n-butyl adipate or solutions of esters of aliphatic acids, e.g. glycols. It may be advantageous for a dispersant known from the pharmaceutical or cosmetic industry also to be present. Examples are pyrrolidin-2-one, N-alkylpyrrolidin-2-one, acetone, polyethylene glycol and its ethers and esters, propylene glycol or synthetic triglycerides.
The oily solutions include e.g. vegetable oils, such as olive oil, groundnut oil, sesame oil, pine oil, linseed oil and castor oil. The vegetable oils may also be in epoxidised form. It is also possible to use paraffins and silicone oils.
Generally a pour-on or spot-on formulation will contain from 1 to 20% by weight of a compound of formula (I), from 0.1 to 50% by weight dispersant and from 45 to 98.9% by weight solvent.
The pour-on or spot-on method can be used especially advantageously for herd animals, such as cattle, horses, sheep and pigs, where it is difficult or time-consuming to treat all the animals orally or via injection. By virtue of its simplicity, this method can of course also be used for all other animals, including individual domestic animals and pets, and is very popular with the keepers of the animals because it can often be carried out without the expert assistance of a veterinary surgeon.
Suitable for parenteral and percutaneous administration are oily injection solutions or suspensions, there being used suitable lipophilic solvents or vehicles, such as fatty oils, for example sesame oil, or synthetic fatty acid esters, for example ethyl oleate, or triglycerides, or aqueous injection solutions or suspensions that comprise viscosity-increasing substances, for example sodium carboxymethylcellulose, sorbitol and/or dextran, and, optionally, stabilisers.
The preparations of the present invention can be prepared in a manner known per se, for example by means of conventional mixing, granulating, confectioning, dissolving or lyophilising processes. For example, pharmaceutical preparations for oral administration can be obtained by combining the active ingredient with solid carriers, optionally granulating the resulting mixture, and processing the mixture or granules, if desired or necessary after the addition of suitable excipients, to form tablets or dragee cores.
The following Examples serve merely to illustrate the invention and do not limit the invention.
Preferred formulations have especially the following composition (throughout, percentages are by weight):
The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
The following Examples illustrate the invention described above but do not limit the scope thereof in any way. Temperatures are given in degrees Celsius. The symbol xe2x80x98hxe2x80x99 stands for xe2x80x98hourxe2x80x99.